1. Field of the Invention
The present invention relates to a series of new bisphenols containing pendent ethynyl groups and new poly(arylene ether)s containing pendent ethynyl groups. These bisphenols are reacted with activated dihalide monomers to form poly(arylene ether)s with pendent ethynyl groups. Upon heating, the pendent ethynyl groups react to form crosslinked resins that are useful as adhesives, composite matrices, moldings and films.
2. Description of Related Art
Poly(arylene ether)s are condensation polymers that can be prepared by various routes. The most popular route involves the reaction of an aromatic bisphenol with an activated aromatic dihalide to form the polymer which has a repeat unit of the general type EQU --O--Ar--O--Ar'--
where Ar is a divalent aromatic radical, which can be as simple as 1,3- or 1,4-disubstituted benzene, or it may be a bis-3 or 4-(diphenylene) having the general structure ##STR1## where X=nil, O, S, SO.sub.2, C.dbd.O, C(CH.sub.3).sub.2, C(CF.sub.3).sub.2, etc. Ar may be any other appropriate divalent radical. Ar' is a divalent aromatic which contains an electron withdrawing activating group para to the halide to be displaced. Ar' has the general structure ##STR2## where X=SO.sub.2, C.dbd.O, etc. ##STR3##
Synthesis and characterization of poly(arylene ether)s containing ethynyl groups have been reported in the literature and summarized in two reviews [P. M. Hergenrother, J. Macromol. Sci. Rev. Macromol. Chem., C19, 1 (1980) and P. M. Hergenrother, in H. Mark, ed., Encyclopedia of Polymer Science and Engineering, 2nd ed., Vol. 1, John Wiley & Sons, Inc., New York, 61 (1985)]. Ethynyl and substituted ethynyl groups have been placed on the ends of oligomers and pendent along the backbone of polymers and thermally reacted to induce chain extension, rigidization, branching and/or crosslinking. More recently, a series of phenylethynyl terminated arylene ether oligomers having good melt stability were prepared and thermally reacted to yield polymers exhibiting excellent solvent resistance and high adhesive properties [R. G. Bryant, B. J. Jensen and P. M. Hergenrother, Polym. Prepr., 33(1), 910 (1992)].